Manufacture of condensation products



Patented Dec. 17, 1935' l UNITED STATES PATENT: OFFICE MANUFACTURE or CONDENSATION raonucrs Leon Lilienield, Vienna, Austria No Drawing. )Applieatlon August 12, 1931, Serial No. 556,718. In Austria September 2, 1930 7 Claims. (Cl. zoo-e) .This invention is based .on the observation that that formaldehyde, polymers of formaldehyde" products of technical value are obtained by con- (for example trioxymethylene, paraformalded-ensing one or more ammonia derivatives of a hyde) and derivatives of formaldehyde, such as thio-carbonic acid, for example thiourea, with hexamethylene-tetramine and acrolein may be an aldehyde, for example formaldehyde, in the used.

presence of a halogen derivative oi a polyhydric The condensation may be carried out in the alcohol (which term is used herein to signify an presence or absence of a basic condensing agent alcohol having two or more -OH groups), or ,(ior exampleammonia, pyridine, a basic salt, an of a derivative, for example an ether, of such alkali metal hydroxide or the like), or in the halogen derivative, or, insteadiorf such halogen presence of an acid condensing agent (for exo derivative, another ester of a polyhydric alcohol, ample a dilute inorganic acid, such as sulphuric for example diacetin or the like; or by bringing acid, glycerine-phosphoric acid or glycerine-sultogether at least one halogen derivat ve of. a phuric acid, or an organic acid, such as tartaric p lyhydric alcohol or a derivative, for example acid or citric acid, or an acid salt), or also in an ether, of such halogen derivative, or another presence of any of the known accelerators. 15

ester of a polyhydric alcohol, with a oondensa- Furthermore, the condensation may be carried tion product of an ammonia derivative of a out in the presence of a phenol or a phenyl-urea thio-carbonic acid, for example thiourea, and an or the like V aldehyde, for example formaldehyde, either dur-' There may be incorporated with the products of ingtheformation of the condensation product 'or the' present invention, in any stage of their pro- 20 after it has already been formed. diiction, any of the softening agents or agents In addition to an ammonia derivative of a imparting plasticity or elasticity, which are' thio-carbonic acid, for example thiourea, there known in the technology of artificial resins or may be used in the present process for the mm in the literature, for example glycerine, glycol, densation with an aldehyde, for example formcyclohexanol or the like. The products of the 25 aldehyde, an ammonia derivative of carbonic invention may also be worked up together with acid, for example urea or dicyanodiamide. another colloid or colloids, such as a natural In comparison with condensation products preresin, rubber or the like.

pared in the absence of a halogen derivative of a The following examples illustrate the invention,

polyhydric alcohol, but otherwise under the same the parts being by weight: 30 conditions, the condensation products obtain- Example 1.--l00 parts of thiourea are mixed able in accordance with the present invention with 170 parts of a commercial solution of form-- 1 have a consid rably i r as d t ndency to r s naldehyde (of about 40 per cen strength) and ify. This resinification occurs in the present 100 partsof a-dichlorhydrin, and the mixture is P r u formly and rapidly than in the heated on a. water bath to 60 C. As soon as this 35 case of a condensation process carried out in temperature isattained, the heating is interruptthe absence of ahalogen derivative of a polyed and the solution, which is completely clear, is hydric alcohol, and the final products of the cooled to 30 C. and allowed to stand at this tempres nt process ass iat with the conversion perature for 20-26 hours. A portion of the clear 40 into the resinous or glassy st re a rule solution is spread ona glass plate and dried at 60 40 more homogeneo more flexible, stronger; more C. until it is no longer sticky and the film appears lustrous and harder than the final products of dry to the touch, The film u obtained is clear,

the corresponding phase of the hitherto known hard and similar to glass. processes These advantages are manifested not f The remainder of the solution is concentrated tifi stttiittttsiiinli tiitii oi oit we consistency; the cm are s worked coatings, or the like. The eflect of the halogen; up e a glass plate into moulfis mto derivatives of polyhydric alcohols or their derivaplates molded articles of any f f i tives cannot be stated with certainty;v it appears, glass plat? mojllditogether h .layer or 5 however, that they take part in the chemical content being maintained at 60 C. until hardenaction whereby the condensation product is l formed. Example 2.-The procedure is as in Example 1,

Among the aldehydes which may be used in' with the exception that there are added to the 45 only in the case of articles such as molded articles, under a reduced pressure at until it is of a 45 accordance with the invention it may be stated mixture of thiourea, dichlorhydrin and formalde- 55 content being maintained at hyde at the commencement 12.5 parts of a solution of ammonia of 25 per cent. strength.

Example 3.The procedure is as in Example 1 or 2, with the exception that the layer spread on the glass plate or the solution orsyrup contained in the mould is hardened at 110 0., whereby the conversion into the resinous or glassy state is considerably accelerated.

Example 4.,The procedure is as in Example 1, or 2, or 3, with the exception that after the reaction mixture has attained a temperature of C., it is not cooled immediately, but is maintained for two hours at 60 C., before it is cooled to 30 C.

Example 5.The procedure is as in Example 1, or 2, or 3, or 4, with the exception that there are added to the solution or syrup, before its conversion into the resinous or glassy state, 34 per cent. of ethylene glycol, calculated on the content of dry material of the solution or syrup.

Example 6.The procedure is as in Example 5, with the exception that there are added in addition-to the ethylene glycol also 4 per cent. of a 50 per cent. solution of glycerine-phosphoric acid, calculated on the content of dry material of the solution or syrup.

Example ?.The procedure is as in any of the parts of a-dichlorhydrin there are used 150-200 parts of dichlorhydrin.

Example 8. parts of thiourea and 79 parts of urea are mixed with 340 10 parts of a-dichlorhydrin, and the mixture is heated on a water bath to 40 C. As soon as this temperature is attained the heating is interruptsolution is cooled to 30 C. and allowed to stand at this temperature for-20-26 hours. A portion of the clear solution is spread on a glass plate and dried at 60 C. until it is no longer sticky and the film appears dry to the touch. The film thus obtained is clear, and hard and similar to glass.

The remainder of the solution is concentrated under a reduced pressure at 40 C. until it is of a syrupy consistency; the clear syrup is then worked up on a glass plate into a film, or in moulds into plates or shaped articles of any desired size, the glass plate or mould, together with the layer or 60 C. until hardening occurs.

Example 9.The procedure is as in Example 8, with the exception that there are addedto the a-dichlorhydrin and formaldehyde at the commencement 12.5 parts of ammonia of 25 per cent. strength.

Example 10. The procedure is as in Example 8, or 9, with the exception that the layer spread on the glass plate or the solution or syrup contained in the mould is hardened at C., whereby the conversion into the resinous or glassy state is considerably accelerated.

Example 11.The procedure is as in Example 8, or 9, or 10, with the exception that there are added to the solution or syrup, before its conversion into the resinous or glassy state, 34 per cent. of ethylene glycol, calculated on the content of dry material of the solution or syrup.

Example 12.The procedure is as in Example mannitolpinaconechlorhydrin, mannitolechlorhydrin, dichlorhydrin, pinacone-chlorhydrin, dichlorhydrin or the like, or a ether (Reboul: sique, 3rd series, Vol. LX) or a-monochlorohydrin ethyl ether (ibidem) or cz-HIOIIOChlOI'OhYdIlIl phenyl ether Berichte der like.

Instead of chlorine derivatives there may also be used bromine or iodine derivatives. As used in the claims, the term an urea body signifies thiourea or its derivatives, alone or mixed with 30 urea or dicyanodiamide.

What I claim is:

1. The process of manufacturing condensation products which comprises chemically combining a mixture consisting of a substance selected from 35 tive of a polyhydric alcohol.

2. The process of manufacturing condensation products which comprises chemically combining 40 a mixture consisting of a substance selected from the group consisting of urea, thiourea and dicyanodiamide, formaldehyde-and a halogen derivative of a polyhydric alcohol.

3. The process of manufacturing condensation products which comprises chemically combining a mixture consisting of thiourea, an aldehyde and dichlorhydrin.

4. A resinous reaction solely of urea, thiourea and dicyanodiamide, an aldehyde and a halogen derivative of a polyhydric alcohol.

5. A resinous reaction product constituted solely of a substance selected from the group consisting. of urea, thiourea and dicyanodiamide, formaldehyde and a halogen derivative of a polyhydric alcohol.

6. A resinous reaction product constituted solely of a substance selected from the group consisting of urea, thiourea and dicyanodiamide, a polymer of formaldehyde and a halogen derivative of a'polyhydric alcohol.

7. A resinous sisting of urea, thiourea. and dicyanodiamide, an aldehyde and dichlorhydrin.

LEON LILIENFELD. 

